CA1107055A - Electrochromic display devices comprising thienylidene pyrazoline compounds - Google Patents
Electrochromic display devices comprising thienylidene pyrazoline compoundsInfo
- Publication number
- CA1107055A CA1107055A CA301,793A CA301793A CA1107055A CA 1107055 A CA1107055 A CA 1107055A CA 301793 A CA301793 A CA 301793A CA 1107055 A CA1107055 A CA 1107055A
- Authority
- CA
- Canada
- Prior art keywords
- pyrazoline
- oxidant
- thienyl
- thienylidene
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Plural Heterocyclic Compounds (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
ELECTROCHROMIC DISPLAY DEVICES COMPRISING
THIENYLIDENE PYRAZOLINE COMPOUNDS
Abstract of the Disclosure This invention relates to a reversible display device based upon the electrochromic properties of certain thienylidene pyrazo-line compounds when used in conjunction with a complementary re-dox material.
THIENYLIDENE PYRAZOLINE COMPOUNDS
Abstract of the Disclosure This invention relates to a reversible display device based upon the electrochromic properties of certain thienylidene pyrazo-line compounds when used in conjunction with a complementary re-dox material.
Description
Field of the Invention The present invention is concerned with a reversible display device which utili~es the electrochromic effect obtained using certa;n thienylidene pyrazoline compounds with complementary redox materials. The thienylidene pyrazoline compounds useful in the present invention are those having the formula R
R - CH ~ CH2 ll ll,R
~ N \S i wherein R equals aryl or aromatic hereto ring and each of Rl and ~ -R2 is hydrogen or lower alkyl.
Prior Art Electrochromic display devices of several ~ypes are known ;n the prior art. As far as we are aware, however, the prior art does not teach the use of the compounds disclosed in the present invention.
Triaryl pyrazoline compounds for use in reversible electrochromic display dev;ces are taught in Canadian patent application 291,872, filed November 28, 1977, inventors ! 1.
., ~ '.
, .
~ 7~SS
Shattuck and Sincerbox. That application, however, contains no disclosure of the thienylidene compounds used in the present invention.
The display devices obtained according to the present invention have the particular advantage over the prior art in having greater electrochromic efficiencies.
Summary of the Invention Thus the present invention provides a reversible electrochromic display device comprising an oxidant/reductant pair in which the oxidant i5 a thienylidene pyrazoline compound having the formula Rl R - CH CH \C C
1 2 ~ R2 N C - CH = CH C C ~
\~ \/
M S
O - C~3 wherein R equals aryl or aromatic hetero ring and each of and R is hydro~en or lower alkylO
In another aspect the present invention provides a reversible electrochromic display device comprising a reactive medium between two electrically conductive electrodes, at least one of which is transparent, said medium comprising an anhydrous solvent and an oxidant/reductant pair in which the reductant is an electron acceptor and the oxidant is a thienylidene pyrazoline compound havlng the formula R -- CH CH2 ~ C C
N C CH = CH C C~
\ N S
wherein R equals a phenyl or thienyl ring which may be sub-stituted with an electron releaslng group and each o~ Rl and R is hydrogen or lower alkyl.
According to one aspect of the present invention, an electrochemical reaction is used to form a color absorbing species. This color forming process is utilized as a display device by containing the reactive medium between electrically conductive electrodes, at least one of which must be trans-parent. In such a configuration, information ls selectively displayed by segmenting the electrodes into a suitable pattern and applying a potential across the proper electrodes to produce coloration in the desired areas.
In the present invention, the electrochromic coloration reaction takes place due to the oxidation of the thienylidene pyrazoline compound at the anode and simultaneous reduction o~ a suitable redox material at the cathode. The thienylidene pyrazoline compound has the formula described above. The useful complementary redox materials are electron acceptors and include such compounds as, for example, phenylhydroquinone, fluorenones, fluorenes, carbazoles which are polynitro sub-stituted, and benzene compounds substituted with electron withdrawing groups. The electron acceptor compound serves as a complementary material in an oxidation/reduction process with the thienylidene pyrazoline. In that oxidation/reduction reaction, the thienylidene pyrazoline compound is oxidized, while the electron acceptor material is reduced, thereby
R - CH ~ CH2 ll ll,R
~ N \S i wherein R equals aryl or aromatic hereto ring and each of Rl and ~ -R2 is hydrogen or lower alkyl.
Prior Art Electrochromic display devices of several ~ypes are known ;n the prior art. As far as we are aware, however, the prior art does not teach the use of the compounds disclosed in the present invention.
Triaryl pyrazoline compounds for use in reversible electrochromic display dev;ces are taught in Canadian patent application 291,872, filed November 28, 1977, inventors ! 1.
., ~ '.
, .
~ 7~SS
Shattuck and Sincerbox. That application, however, contains no disclosure of the thienylidene compounds used in the present invention.
The display devices obtained according to the present invention have the particular advantage over the prior art in having greater electrochromic efficiencies.
Summary of the Invention Thus the present invention provides a reversible electrochromic display device comprising an oxidant/reductant pair in which the oxidant i5 a thienylidene pyrazoline compound having the formula Rl R - CH CH \C C
1 2 ~ R2 N C - CH = CH C C ~
\~ \/
M S
O - C~3 wherein R equals aryl or aromatic hetero ring and each of and R is hydro~en or lower alkylO
In another aspect the present invention provides a reversible electrochromic display device comprising a reactive medium between two electrically conductive electrodes, at least one of which is transparent, said medium comprising an anhydrous solvent and an oxidant/reductant pair in which the reductant is an electron acceptor and the oxidant is a thienylidene pyrazoline compound havlng the formula R -- CH CH2 ~ C C
N C CH = CH C C~
\ N S
wherein R equals a phenyl or thienyl ring which may be sub-stituted with an electron releaslng group and each o~ Rl and R is hydrogen or lower alkyl.
According to one aspect of the present invention, an electrochemical reaction is used to form a color absorbing species. This color forming process is utilized as a display device by containing the reactive medium between electrically conductive electrodes, at least one of which must be trans-parent. In such a configuration, information ls selectively displayed by segmenting the electrodes into a suitable pattern and applying a potential across the proper electrodes to produce coloration in the desired areas.
In the present invention, the electrochromic coloration reaction takes place due to the oxidation of the thienylidene pyrazoline compound at the anode and simultaneous reduction o~ a suitable redox material at the cathode. The thienylidene pyrazoline compound has the formula described above. The useful complementary redox materials are electron acceptors and include such compounds as, for example, phenylhydroquinone, fluorenones, fluorenes, carbazoles which are polynitro sub-stituted, and benzene compounds substituted with electron withdrawing groups. The electron acceptor compound serves as a complementary material in an oxidation/reduction process with the thienylidene pyrazoline. In that oxidation/reduction reaction, the thienylidene pyrazoline compound is oxidized, while the electron acceptor material is reduced, thereby
- 2(a) -~7V~i 1 tending to balance the display cell electrochemically. This 2 electrochemical balance results in good reversibility of
3 cell operation. Still another advantage is a reduction of
4 electrode degradation. ~ncreased color change may also be obtained due to color produced by the reduced form of the 6 complementary redox material, in addition to the oxidized 7 thienylidene pyra201ine. Erasure of the image is obtained 8 in a symmetrical cell by short-circuiting the cell or by 9 momentary application of the reverse polarity potential.
As is known to the prior art, the electrochromic 11 reaction is carried out in an anhydrous solvent. Useful 12 solvents include, for example, methyl ethyl ketone, N,N-di-13 methylformamide, dimethylsulfoxide, N,N-dimethylacetamide, L~ tetrahydrofuran, and acetonitrile.
The thienylidene pyrazoline compounds of the present 16 invention are those having the formula 17 R\
19 ~ N\ ~C - CH - CH - & C
2~ wherein R equals aryl or aromatic hetero ring and each of ~3 and R is hydrogen or lower alkyl.
~4 As examples of compounds having the above formula which have been found particularly useful in the present invention 26 mention is made of 1-p-anisyl-3-[2-(3-methyl-2-thienyl) 27 vinyl]-5-p-diethylamino phenyl ~-2-pyrazoline; l-p anisyl-3-28 [2-(5-methyl-2-thienyl)-vinyl]-5-p-diethylamino phenyl ~-2-29 pyrazoline; 1-p-anisyl-3-[2 (3-methyl-2-thienyl)-vinyl]-5-[3-methyl-2-thienyl] ~-2-pyrazoline; 1-p-anisyl-3-[2-(3 methyl-SA976021 -3~
u~
1 2-thienyl)~vinyl]-5-phenyl ~-2-pyrazoline; and l-p-anisyl-' 2 3-[2-(2-thienyl)-vinyl]-5-[2thienyl] ~-2-pyrazoline.
3 Particular attention also should be called to the require-4 ment of a phenyl group with a methoxy substituent in the para position. Only when the molecules hava this particular con-6 figuration are the very great efficiencies of the present 7 invention obtained. The theoretical explanation for this is 8 not understood.
g The following Examples are given solely for purposes of illustration and are not to be considered limitations on the 11 invention, many variations of which are possible without 12 departing from the spirit or scope thereof.
13 ,EXAMPLE I
14 A solution is made up of 0.1 molar phenyl-p-benzoquinone;
16 0.1 molar E ,N - ~ - CH - CH2 CH
17 ~ N ~ ~ - CH = CH - ¦
and 0.4 molar Tetrabutylammonium tetrafluoborate 21 in methyl èthyl ketone.
22 The above solution is placed between two transparent 23 In2 O3 electrodes 5 mils apart and a potential is applied 24 across the cell. A color change from yellow to brownish-black is observed and when the potential is removed the color returns 26 to the yellow state~
28 Example 1 is repeated using 29 .8 molar tetrabutyl ammonium tetrafluohorate instead of 0.4 molar and using the solvent system 76~
1 methyl ethyl ketone/acetonitrile/ethanol in a 3 to 2 1 to 1 ratio.
3 Again the solution is placed between two transparent 4 In2 3 electrodes with 5 mil spacing and a potential of about 2 volts is placed across the cell. The optical density is 6 measured by a photopic probe apparatus which simulates the 7 sensitivity of the human eye (5500 A peak sensitivity). The 8 current across the cell is mea~ured for a known length of time.
9 Thereby, one can compute the milli coulombs/cm2 passed through the cell to give a certain optical density. This optical 11 density per milli coulombs per centimeter squared is termed 12 the efficiency of the cell. In this example, the efficiency 13 is 0.291 OD/MC/cm .
EXAMPLE III
16 The following solution is prepared by dissolving the 17 solid ingredients in a 3:1:1 solvent system of methyl ethyl 18 ketone/acetonitrile/ethanol.
19 The solids are:
.1 molar ,N - ~ - CH CH2 22 OC~3 N \ ~ - C3 = C3-24 and .1 molar p-nitrobenzonitrile, and .8 molar Tetrabutylammonium tetrafluoborate 26 The material is tested as in the previous Example and an 27 efficiency of 0.322 OD/MC/cm is obtained.
SA976021 ~5-
As is known to the prior art, the electrochromic 11 reaction is carried out in an anhydrous solvent. Useful 12 solvents include, for example, methyl ethyl ketone, N,N-di-13 methylformamide, dimethylsulfoxide, N,N-dimethylacetamide, L~ tetrahydrofuran, and acetonitrile.
The thienylidene pyrazoline compounds of the present 16 invention are those having the formula 17 R\
19 ~ N\ ~C - CH - CH - & C
2~ wherein R equals aryl or aromatic hetero ring and each of ~3 and R is hydrogen or lower alkyl.
~4 As examples of compounds having the above formula which have been found particularly useful in the present invention 26 mention is made of 1-p-anisyl-3-[2-(3-methyl-2-thienyl) 27 vinyl]-5-p-diethylamino phenyl ~-2-pyrazoline; l-p anisyl-3-28 [2-(5-methyl-2-thienyl)-vinyl]-5-p-diethylamino phenyl ~-2-29 pyrazoline; 1-p-anisyl-3-[2 (3-methyl-2-thienyl)-vinyl]-5-[3-methyl-2-thienyl] ~-2-pyrazoline; 1-p-anisyl-3-[2-(3 methyl-SA976021 -3~
u~
1 2-thienyl)~vinyl]-5-phenyl ~-2-pyrazoline; and l-p-anisyl-' 2 3-[2-(2-thienyl)-vinyl]-5-[2thienyl] ~-2-pyrazoline.
3 Particular attention also should be called to the require-4 ment of a phenyl group with a methoxy substituent in the para position. Only when the molecules hava this particular con-6 figuration are the very great efficiencies of the present 7 invention obtained. The theoretical explanation for this is 8 not understood.
g The following Examples are given solely for purposes of illustration and are not to be considered limitations on the 11 invention, many variations of which are possible without 12 departing from the spirit or scope thereof.
13 ,EXAMPLE I
14 A solution is made up of 0.1 molar phenyl-p-benzoquinone;
16 0.1 molar E ,N - ~ - CH - CH2 CH
17 ~ N ~ ~ - CH = CH - ¦
and 0.4 molar Tetrabutylammonium tetrafluoborate 21 in methyl èthyl ketone.
22 The above solution is placed between two transparent 23 In2 O3 electrodes 5 mils apart and a potential is applied 24 across the cell. A color change from yellow to brownish-black is observed and when the potential is removed the color returns 26 to the yellow state~
28 Example 1 is repeated using 29 .8 molar tetrabutyl ammonium tetrafluohorate instead of 0.4 molar and using the solvent system 76~
1 methyl ethyl ketone/acetonitrile/ethanol in a 3 to 2 1 to 1 ratio.
3 Again the solution is placed between two transparent 4 In2 3 electrodes with 5 mil spacing and a potential of about 2 volts is placed across the cell. The optical density is 6 measured by a photopic probe apparatus which simulates the 7 sensitivity of the human eye (5500 A peak sensitivity). The 8 current across the cell is mea~ured for a known length of time.
9 Thereby, one can compute the milli coulombs/cm2 passed through the cell to give a certain optical density. This optical 11 density per milli coulombs per centimeter squared is termed 12 the efficiency of the cell. In this example, the efficiency 13 is 0.291 OD/MC/cm .
EXAMPLE III
16 The following solution is prepared by dissolving the 17 solid ingredients in a 3:1:1 solvent system of methyl ethyl 18 ketone/acetonitrile/ethanol.
19 The solids are:
.1 molar ,N - ~ - CH CH2 22 OC~3 N \ ~ - C3 = C3-24 and .1 molar p-nitrobenzonitrile, and .8 molar Tetrabutylammonium tetrafluoborate 26 The material is tested as in the previous Example and an 27 efficiency of 0.322 OD/MC/cm is obtained.
SA976021 ~5-
5~
2 Example III is repeated usiny a solvent system of 3 methyl ethyl ketone/ethanol in a 4:1 ratio and substituting 4 phenyl-p-benzoquinone for p-nitrobenzonikrile. Efficiency is 0.297 OD/MC/cm2.
7 ExAMæLE V
8 The following solution is prepared:
9 .17 molar Et`N - ~ - CH - CH
11 ~ N\ ~ - CH = CH- ~ H3 13 .3 molar phenyl-p-benzoquinone~ and 14 .4 molar tetrabutylammonium perchlorate in methyl ethyl ketone. When tested as shown in Example II
16 an efficiency of .287 OD/MC/cm2 is obtained.
. _ 19 Two electrochromic solutions were prepared for a com-parative test in order to show the improved efficiency of a 21 compound of the present invention, when compared to a related 22 compound not having a thienylidene group.
23 Solution A Solution B
_ _ 24 Q.15 molar .15 molar Et,N ~ fH-CH2 Et_N ~ -CH-CH2 t 26 N ~ -CH=CH~ N / -CH=CH ~ -N-E
27 ~ N `S~ `CH ~ N ~=J `Ek ~ ~7 ~
1 .06 molar phenyl-p-benzoquinone .06 molar phenyl-p-benzoquinone 2 .13 molar tetraethylammonium .13 molar tetraethylammonium 3 tetrafluoborate tetrafluoborate 4 - N~N-dimethylacetamide - N,N-dimethylacetamide Efficiency: 0~299 OD/MC/cm .252 OD/MC/cm 8 A solution was prepared using the following materials:
9 .15 molar 0 - CH - CH2 11 ~ N ~1_ CH = CH-13 .06 molar phenyl-p~b~nzoquinone 14 .13 molar tetraethylammonium tetrafluoborate dimethylacetamide 16 Efficiency as measured in the previous Examples is 0.209 17 OD/MC/cm .
The following two solutions are prepared varying only 21 in pyrazoline compound.
22 A- B.
224 ~ - CH - CH fCH3 C~
26 N ~ -CH = CH ~ N ~ -C~ = CH ~S ~
27 OCH3 OCH~
28 0.2 grams 0.2 grams 29 0.2 grams tetraethylammonium tetrafluoborate 0.1 grams p-nitrobenzonitrile in N-methyl pyrrolidone.
7~5 l Optical Density 0.46 0.44 2 Voltage on Circuit 6 V 6 V
3 Time on 88 msPc 68 msec 4 Color Black Black S Eficiency 0.18 OD/MC/cm .22 OD/MC/cm2 8 The following formulation was tested for various g electrochromic parameters.
1~
ll ~158 molar -N- ~ -CH - CH CH3 12 ~ ~ N~ -CH = CH-.25 molar p-nitrobenzonitrile 16 1.2 molar tetrabutyl ammonium tetrafluoborate 17 in methyl ethyl ketone.
19 The following parameters were measured.
OD/V slope 0.55 21 Threshold voltage 1.24 22 Ave. Efficiency , .72 OD/MC/cm2 23 Pulse Time 2 milliseconds 24 OD @ 2.0 V 0.41 Electrode spacing 1.5 mils .....
28 Using the procedure described above, the following com-29 pounds were measured for electrochromium efficiency~ These tests show the very great advantage of having a methoxy group SA97602l -8-``--1 in the compound.
2 StructUre Efficienc~
3 1. _N- ~ -fH - CH X = H .05 OD/MC/cm N ~ -CH = CH- ~ -CH3 X OCH3
2 Example III is repeated usiny a solvent system of 3 methyl ethyl ketone/ethanol in a 4:1 ratio and substituting 4 phenyl-p-benzoquinone for p-nitrobenzonikrile. Efficiency is 0.297 OD/MC/cm2.
7 ExAMæLE V
8 The following solution is prepared:
9 .17 molar Et`N - ~ - CH - CH
11 ~ N\ ~ - CH = CH- ~ H3 13 .3 molar phenyl-p-benzoquinone~ and 14 .4 molar tetrabutylammonium perchlorate in methyl ethyl ketone. When tested as shown in Example II
16 an efficiency of .287 OD/MC/cm2 is obtained.
. _ 19 Two electrochromic solutions were prepared for a com-parative test in order to show the improved efficiency of a 21 compound of the present invention, when compared to a related 22 compound not having a thienylidene group.
23 Solution A Solution B
_ _ 24 Q.15 molar .15 molar Et,N ~ fH-CH2 Et_N ~ -CH-CH2 t 26 N ~ -CH=CH~ N / -CH=CH ~ -N-E
27 ~ N `S~ `CH ~ N ~=J `Ek ~ ~7 ~
1 .06 molar phenyl-p-benzoquinone .06 molar phenyl-p-benzoquinone 2 .13 molar tetraethylammonium .13 molar tetraethylammonium 3 tetrafluoborate tetrafluoborate 4 - N~N-dimethylacetamide - N,N-dimethylacetamide Efficiency: 0~299 OD/MC/cm .252 OD/MC/cm 8 A solution was prepared using the following materials:
9 .15 molar 0 - CH - CH2 11 ~ N ~1_ CH = CH-13 .06 molar phenyl-p~b~nzoquinone 14 .13 molar tetraethylammonium tetrafluoborate dimethylacetamide 16 Efficiency as measured in the previous Examples is 0.209 17 OD/MC/cm .
The following two solutions are prepared varying only 21 in pyrazoline compound.
22 A- B.
224 ~ - CH - CH fCH3 C~
26 N ~ -CH = CH ~ N ~ -C~ = CH ~S ~
27 OCH3 OCH~
28 0.2 grams 0.2 grams 29 0.2 grams tetraethylammonium tetrafluoborate 0.1 grams p-nitrobenzonitrile in N-methyl pyrrolidone.
7~5 l Optical Density 0.46 0.44 2 Voltage on Circuit 6 V 6 V
3 Time on 88 msPc 68 msec 4 Color Black Black S Eficiency 0.18 OD/MC/cm .22 OD/MC/cm2 8 The following formulation was tested for various g electrochromic parameters.
1~
ll ~158 molar -N- ~ -CH - CH CH3 12 ~ ~ N~ -CH = CH-.25 molar p-nitrobenzonitrile 16 1.2 molar tetrabutyl ammonium tetrafluoborate 17 in methyl ethyl ketone.
19 The following parameters were measured.
OD/V slope 0.55 21 Threshold voltage 1.24 22 Ave. Efficiency , .72 OD/MC/cm2 23 Pulse Time 2 milliseconds 24 OD @ 2.0 V 0.41 Electrode spacing 1.5 mils .....
28 Using the procedure described above, the following com-29 pounds were measured for electrochromium efficiency~ These tests show the very great advantage of having a methoxy group SA97602l -8-``--1 in the compound.
2 StructUre Efficienc~
3 1. _N- ~ -fH - CH X = H .05 OD/MC/cm N ~ -CH = CH- ~ -CH3 X OCH3
6 X
9 S ICH - CH2 X = H .03 OD/MC/cm ~ N~ ~ -CH = CH _ ~ X = OCH3 .18 OD/MC/cm lL X
13 3 Et_N ~ -CH - CIH~ C ~ X = H .05 OD/MC/cm ~ N ~ -CH - CH - I X = OCH3 .29 OD/MC/cm 19 A typical synthesis of thienylidene pyrazolines is outlined below.
21 Et~N ~ -C~ + CH3-C-CH3 NaOH Et~N ~ -CH = CH C CH
22 H EtOH Et ~ 3 23 (excess) Et~ ~ ,O, O N OH
28 ~N ~ -CH = CH-C-CH - CH~ CH3 2g
9 S ICH - CH2 X = H .03 OD/MC/cm ~ N~ ~ -CH = CH _ ~ X = OCH3 .18 OD/MC/cm lL X
13 3 Et_N ~ -CH - CIH~ C ~ X = H .05 OD/MC/cm ~ N ~ -CH - CH - I X = OCH3 .29 OD/MC/cm 19 A typical synthesis of thienylidene pyrazolines is outlined below.
21 Et~N ~ -C~ + CH3-C-CH3 NaOH Et~N ~ -CH = CH C CH
22 H EtOH Et ~ 3 23 (excess) Et~ ~ ,O, O N OH
28 ~N ~ -CH = CH-C-CH - CH~ CH3 2g
7~
Et~ o N~-cH=cH-c-cH=cH~ S' -CH3 2 (~ -OCH3 . HC1 ETOH
Et 4 N- r3 -CH--CH
6 Et ,~ N ~ ~ -CH - CH~ CH
Et~ o N~-cH=cH-c-cH=cH~ S' -CH3 2 (~ -OCH3 . HC1 ETOH
Et 4 N- r3 -CH--CH
6 Et ,~ N ~ ~ -CH - CH~ CH
Claims (7)
1. A reversible electrochromic display device comprising an oxidant/reductant pair in which the oxidant is a thienylidene pyrazoline compound having the formula = wherein R equals aryl or aromatic hetero ring and each of R1 and R2 is hydrogen or lower alkyl.
2. A reversible electrochromic display device as in Claim 1, comprising a reactive medium between two electrically conductive electrodes, at least one of which is transparent, said medium comprising an anhydrous solvent and an oxidant/-reductant pair in which the reductant is an electron acceptor and the oxidant is a thienylidene pyrazoline compound having the formula = wherein R equals a phenyl or thienyl ring which may be sub-stituted with an electron releasing group and each of R1 and R2 is hydrogen or lower alkyl.
3. A device as claimed in claim 1 or 2 wherein the oxidant is 1-p-anisyl-3-[2-(3-methyl-2-thienyl)-vinyl]-5-p-die-thylamino phenyl .DELTA.-2-pyrazoline.
4. A device as claimed in claim 1 or 2 wherein the oxidant is 1-p-anisyl-3-[2-(5-methyl-2-thienyl)-vinyl]-5-p-die-thylamino phenyl .DELTA.-2-pyrazoline.
5. A device as claimed in claim 1 or 2 wherein the oxidant is 1-p-anisyl-3-[2-(3-methyl-2-2-thienyl)-vinyl]-5-[3-methyl-2-thienyl] .DELTA.-2-pyrazoline.
6. A device as claimed in claim 1 or 2 wherein the oxidant is 1-p-anisyl-3-[2-(3-methyl-2-thienyl)-vinyl]-5-phenyl .DELTA.-2-pyrazoline.
7. A device as claimed in claim 1 or 2 wherein the oxidant is 1-p-anisyl-3-[2-(2-thienyl)-vinyl]-5-[2-thienyl] .DELTA.-2-pyrazoline.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US801,946 | 1977-05-31 | ||
| US05/801,946 US4090782A (en) | 1977-05-31 | 1977-05-31 | Electrochromic display devices comprising thienylidene pyrazoline compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1107055A true CA1107055A (en) | 1981-08-18 |
Family
ID=25182422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA301,793A Expired CA1107055A (en) | 1977-05-31 | 1978-04-24 | Electrochromic display devices comprising thienylidene pyrazoline compounds |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4090782A (en) |
| JP (1) | JPS5835551B2 (en) |
| AT (1) | AT358109B (en) |
| CA (1) | CA1107055A (en) |
| DE (1) | DE2823212A1 (en) |
| FR (1) | FR2393029A1 (en) |
| GB (1) | GB1603179A (en) |
| IT (1) | IT1113176B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4249013A (en) * | 1979-01-26 | 1981-02-03 | Bell Telephone Laboratories, Incorporated | Conjugatively linked tetrathiafulvalenes and method for preparation thereof |
| US4309081A (en) * | 1979-05-29 | 1982-01-05 | Bell Telephone Laboratories, Incorporated | Display devices |
| GB8517622D0 (en) * | 1985-07-12 | 1985-08-21 | Secr Defence | Electrically conducting conjugated polymers |
| GB8602708D0 (en) * | 1986-02-04 | 1986-03-12 | Ici Plc | Non-linear optics |
| GB8602706D0 (en) * | 1986-02-04 | 1986-03-12 | Ici Plc | Non-linear optics |
| US5128799B1 (en) * | 1986-03-31 | 1996-11-05 | Gentex Corp | Variable reflectance motor vehicle mirror |
| US5282077A (en) * | 1986-03-31 | 1994-01-25 | Gentex Corporation | Variable reflectance mirror |
| US4902108A (en) * | 1986-03-31 | 1990-02-20 | Gentex Corporation | Single-compartment, self-erasing, solution-phase electrochromic devices, solutions for use therein, and uses thereof |
| US5151816A (en) * | 1989-12-29 | 1992-09-29 | Donnelly Corporation | Method for reducing current leakage and enhancing uv stability in electrochemichromic solutions and devices |
| US5140455A (en) | 1989-11-29 | 1992-08-18 | Donnelly Corporation | High performance electrochemichromic solutions and devices thereof |
| US5142407A (en) * | 1989-12-22 | 1992-08-25 | Donnelly Corporation | Method of reducing leakage current in electrochemichromic solutions and solutions based thereon |
| US5145609A (en) * | 1990-11-07 | 1992-09-08 | Donnelly Corporation | Linear polyether-containing electrochemichromic solutions and related devices |
| US5239405A (en) * | 1991-09-06 | 1993-08-24 | Donnelly Corporation | Electrochemichromic solutions, processes for preparing and using the same, and devices manufactured with the same |
| US5233461A (en) * | 1991-09-06 | 1993-08-03 | Donnelly Corporation | Methods for sealing electrochromic devices and devices manufactured thereby |
| US5500760A (en) * | 1991-09-06 | 1996-03-19 | Donnelly Corporation | Electrochemichromic solutions, processes for preparing and using the same, and devices manufactured with the same |
| US5471337A (en) * | 1994-08-25 | 1995-11-28 | The Dow Chemical Company | Photostable self-erasing electrochromic device |
| US5671082A (en) * | 1994-08-25 | 1997-09-23 | The Dow Chemical Company | Single compartment self-erasing electrochromic device |
| DE19605448A1 (en) * | 1996-02-15 | 1997-08-21 | Bayer Ag | Electrochromic system |
| DE19605451A1 (en) * | 1996-02-15 | 1997-08-21 | Bayer Ag | Electrochromic system |
| US7064212B2 (en) * | 2002-06-20 | 2006-06-20 | The Regents Of The University Of California | Electrochromic salts, solutions, and devices |
| WO2008146405A1 (en) * | 2007-06-01 | 2008-12-04 | Nippon Chemical Works Co., Ltd. | Fluorescent material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3180729A (en) * | 1956-12-22 | 1965-04-27 | Azoplate Corp | Material for electrophotographic reproduction |
| US3451741A (en) * | 1966-06-15 | 1969-06-24 | Du Pont | Electrochromic device |
| NL166053C (en) * | 1970-06-27 | 1981-06-15 | Philips Nv | IMAGE DISPLAY DEVICE. |
| BE793156A (en) * | 1971-12-23 | 1973-06-21 | Philips Nv | IMAGE REPRODUCING CELL |
| US3824099A (en) * | 1973-01-15 | 1974-07-16 | Ibm | Sensitive electrophotographic plates |
| US3837851A (en) * | 1973-01-15 | 1974-09-24 | Ibm | Photoconductor overcoated with triarylpyrazoline charge transport layer |
| NL7411935A (en) * | 1973-09-21 | 1975-03-25 | Matsushita Electric Ind Co Ltd | COLOR DISPLAY DEVICE. |
| GB1506560A (en) * | 1974-03-15 | 1978-04-05 | Ici Ltd | Device |
| US3957352A (en) * | 1975-09-02 | 1976-05-18 | Timex Corporation | Electrochromic display having improved electrolyte |
-
1977
- 1977-05-31 US US05/801,946 patent/US4090782A/en not_active Expired - Lifetime
-
1978
- 1978-03-31 JP JP53036926A patent/JPS5835551B2/en not_active Expired
- 1978-04-05 FR FR7813745A patent/FR2393029A1/en active Granted
- 1978-04-24 CA CA301,793A patent/CA1107055A/en not_active Expired
- 1978-05-05 IT IT23047/78A patent/IT1113176B/en active
- 1978-05-10 GB GB18840/78A patent/GB1603179A/en not_active Expired
- 1978-05-26 AT AT386378A patent/AT358109B/en not_active IP Right Cessation
- 1978-05-27 DE DE19782823212 patent/DE2823212A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IT7823047A0 (en) | 1978-05-05 |
| GB1603179A (en) | 1981-11-18 |
| JPS53147688A (en) | 1978-12-22 |
| FR2393029B1 (en) | 1980-10-10 |
| AT358109B (en) | 1980-08-25 |
| IT1113176B (en) | 1986-01-20 |
| JPS5835551B2 (en) | 1983-08-03 |
| FR2393029A1 (en) | 1978-12-29 |
| US4090782A (en) | 1978-05-23 |
| DE2823212A1 (en) | 1978-12-14 |
| ATA386378A (en) | 1980-01-15 |
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